CN103571449A - Clay stabilizer for long-acting oil wells and preparation and applications thereof - Google Patents

Clay stabilizer for long-acting oil wells and preparation and applications thereof Download PDF

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Publication number
CN103571449A
CN103571449A CN201310552134.XA CN201310552134A CN103571449A CN 103571449 A CN103571449 A CN 103571449A CN 201310552134 A CN201310552134 A CN 201310552134A CN 103571449 A CN103571449 A CN 103571449A
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China
Prior art keywords
clay stabilizer
long
clay
acting oil
oil well
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CN201310552134.XA
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CN103571449B (en
Inventor
刘锦
杨华
慕立俊
赵振峰
李宪文
张矿生
唐梅荣
薛小佳
吕海燕
吴江
范华波
周晓群
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China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

The invention relates to a clay stabilizer for long-acting oil wells and preparation and applications thereof. The clay stabilizer is prepared by the steps of: adding epoxy chloropropane and short-chain multi-charged cation polyquaternium into a reactor in a mole ratio of 1-2:1, and simultaneously adding 5-15% by mass of a solvent and 1-5% by mass of a catalyst; stirring, heating to 30-100 DEG C, and reacting 2-6 hours so as to obtain colorless transparent liquid, namely, the clay stabilizer for long-acting oil wells. The clay stabilizer is relatively small in molecular weight and small in molecular size range, so that a situation that the clay stabilizer blocks a micropore throat of a tight reservoir can be prevented, thereby reducing the harm to the permeability of a low-permeability oil layer; a main agent of the clay stabilizer contains multiple cation points, so that the number of bonding points of the clay stabilizer molecule and the reservoir is further improved, and the anti-swelling performance is improved; the preparation process is simple, and materials are easily obtained; the clay stabilizer can endow a fracturing fluid system with a long-acting clay stabilizing performance.

Description

A kind of clay stabilizer and preparation and application for long-acting oil well
Technical field
The present invention relates to field of petroleum exploitation, long-acting clay stabilizer and preparation and application that particularly the oily reservoir wellfracturing of a kind of applicable densification yield-increasing technique is used.
Background technology
The fine and close hydrocarbon resources of China is abundant, is mainly distributed in the basins such as Erdos, Sichuan, pine the Liao Dynasty, Bohai Sea Gulf, Zhunger Basin, and exploration evaluation shows that only fine and close oily total resources reaches 110～13,500,000,000 tons.Along with the continuous progress of exploratory development technology, the particularly breakthrough of horizontal well volume fracturing technology, fine and close oil exploitation is celebrated oil field, Daqing oil field and tells the oil fields such as Kazakhstan and carry out Pilot trial long.
Fine and close oily reservoir CLAY MINERALS AND THEIR SIGNIFICANCE complicated component, these clay minerals are many to be comprised of silicon-oxy tetrahedron and alumina octahedral, and interlayer surface is zone of oxidation, a little less than connecting forces.When contacting with water, tradable Si in clay mineral 4+, Al 3+positively charged ion in water respectively by Al 3+and Fe 2+, Mg 2+positively charged ion replaces, and has produced thus superfluous negative charge, makes mutually to repel between crystal layer, causes clay swelling, dispersion, and migrates under the impulse force of current.Fine and close oily reservoir reconstruction is mainly on a large scale at present, discharge capacity, low sand ratio, low gluing are taken sand greatly, in this large-scale waterfrac treatment construction process, a large amount of aqueous solution and clay contacting, make clay expand, disperse and migrate, and then reduce reservoir permeability or stop up reservoir passage.Therefore be necessary to improve with clay stabilizer the anti-swollen rate of operation liquid, reduce clay dispersion migration, improve reservoir permeability.
Conventional clay stabilizer is positively charged ion, quaternary surfactant, polyamine and the polyquaternary amine etc. with a plurality of electric charges.Above clay stabilizer all can suppress clay swelling and migration, but has some problems: multi-charge positively charged ion needs suitable spearhead and subsequent fluid in pressing crack construction, easily causes obstruction; It is glossy wet that quaternary surfactant can make silicate become, thereby reduce the relative permeability of hydrocarbon in rock; The validity period of polyamine class clay stabilizer is short, and expense is high; The conference of polyquaternary amine class relative molecular weight increases the weight of the injury to low permeability pay rate of permeation.
Summary of the invention
The object of this invention is to provide a kind of have long-lasting, high adsorption capacity, relative molecular mass little, to adaptable clay stabilizer and preparation and the application for long-acting oil well in stratum, prevent clay mineral hydration swelling, disperse migration, reduce the injury to low permeability pay rate of permeation.
The preparation method of clay stabilizer for long-acting oil well of the present invention:
Adopt epoxy chloropropane and the reaction of short chain multi-charge positively charged ion polyquaternium, add the solvent of 5-15% weight and the initiator of 1-5% weight simultaneously, stirring is warming up to 30-100 ℃, reaction 2-6 hour, make colourless transparent liquid and be long-acting oil well clay stabilizer, oxygen chloropropane and short chain multi-charge positively charged ion polyquaternium mol ratio are 1～2:1.
Described short chain multi-charge positively charged ion polyquaternium is white powder or particle, and its molecular weight is 2-10 ten thousand, and cationic degree is 10%-20%.
Described solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol.
Described initiator is Potassium hydrogen sulfite, Sodium Persulfate, ferric ammonium sulfate, a kind of in S-WAT.
The invention has the beneficial effects as follows:
1. long-acting oil well of the present invention is little with clay stabilizer relative molecular weight, and molecular dimension scope distributes little, can prevent that clay stabilizer from stopping up compact reservoir micropore larynx, alleviates the injury to low permeability pay rate of permeation.
2. in clay stabilizer of the present invention, host contains a plurality of positively charged ion points, has further promoted the binding site number of clay stabilization agent molecule and reservoir, has improved anti-swollen performance.
3. clay stabilizer of the present invention can be difficult for decomposing by a plurality of attachment point strong adsorption at surface of clay, and the validity period of clay stabilizer is long.
4. clay stabilizer of the present invention and fracturing liquid compatibility are good, and in fracturing base fluid, adding volumetric concentration is that 0.5% clay stabilizer generates without precipitation.
5. the raw material that the present invention uses is easy to get, and preparation process is simple.
Embodiment
Below by specific embodiment, the present invention is explained.
Embodiment 1:
The there-necked flask that magnetic agitation, thermometer are housed is placed in to magnetic stirring apparatus control-temperature electric heating to be put, to adding mol ratio in there-necked flask, be epoxy chloropropane and the short chain multi-charge positively charged ion polyquaternium of 2:1, add the ethanol of 10% weight and the S-WAT of 2% weight simultaneously, stirring is warming up to 70 ℃, continue to stir 5 hours, obtain colourless transparent liquid and be long-acting oil well clay stabilizer.
Embodiment 2:
The there-necked flask that magnetic agitation, thermometer are housed is placed in to magnetic stirring apparatus control-temperature electric heating to be put, to adding mol ratio in there-necked flask, be epoxy chloropropane and the short chain multi-charge positively charged ion polyquaternium of 1.8:1, add the methyl alcohol of 10% weight and the Potassium hydrogen sulfite of 2% weight simultaneously, stirring is warming up to 80 ℃, continue to stir 4 hours, obtain colourless transparent liquid and be long-acting oil well clay stabilizer.
Embodiment 3:
The there-necked flask that magnetic agitation, thermometer are housed is placed in to magnetic stirring apparatus control-temperature electric heating to be put, to adding mol ratio in there-necked flask, be epoxy chloropropane and the short chain multi-charge positively charged ion polyquaternium of 1.0:1, add the Virahol of 10% weight and the S-WAT of 2% weight simultaneously, stirring is warming up to 70 ℃, continue to stir 6 hours, obtain colourless transparent liquid and be long-acting oil well clay stabilizer.
Embodiment 4:
The there-necked flask that magnetic agitation, thermometer are housed is placed in to magnetic stirring apparatus control-temperature electric heating to be put, to adding mol ratio in there-necked flask, be epoxy chloropropane and the short chain multi-charge positively charged ion polyquaternium of 1.2:1, add the ethanol of 10% weight and the Sodium Persulfate of 2% weight simultaneously, stirring is warming up to 80 ℃, continue to stir 6 hours, obtain colourless transparent liquid and be long-acting oil well clay stabilizer.

Claims (4)

1. a preparation method for clay stabilizer for long-acting oil well, is characterized in that:
By epoxy chloropropane and short chain multi-charge positively charged ion polyquaternium, be that 1～2:1 adds reactor in molar ratio, add the solvent of 5-15% weight and the initiator of 1-5% weight simultaneously, stirring is warming up to 30-100 ℃, reaction 2-6 hour, makes colourless transparent liquid and is long-acting oil well clay stabilizer.
2. the preparation method of clay stabilizer for long-acting oil well according to claim 1, is characterized in that: described short chain multi-charge positively charged ion polyquaternium is white powder or particle, and its molecular weight is 2-10 ten thousand, and cationic degree is 10%-20%.
3. a long-acting oil well clay stabilizer, is characterized in that: it is to be prepared by the preparation method of clay stabilizer by long-acting oil well claimed in claim 1.
4. an application for clay stabilizer for long-acting oil well claimed in claim 3, is characterized in that: as oil well clay stabilizer, during use, in fracturing base fluid, adding volumetric concentration is 0.5% clay stabilizer.
CN201310552134.XA 2013-11-08 2013-11-08 A kind of long-acting oil well clay stabilizer and preparation thereof and application Active CN103571449B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108329902A (en) * 2018-01-23 2018-07-27 中国石油天然气股份有限公司 A kind of salt tolerant clay stabilizer and preparation method thereof of oil field water outlet preparing fracturing fluid
US10351760B2 (en) 2014-07-15 2019-07-16 Halliburton Energy Services, Inc. Polymeric ionic liquid clay control agents
CN111471440A (en) * 2020-05-28 2020-07-31 陕西科技大学 Multi-cation anti-swelling agent and preparation method and application thereof
CN112251213A (en) * 2020-10-15 2021-01-22 中国地质科学院水文地质环境地质研究所 Composite chemical stimulant in geothermal system
CN114989801A (en) * 2022-06-15 2022-09-02 胜利油田华滨化工有限责任公司 Small cation clay stabilizer and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102676148A (en) * 2012-05-25 2012-09-19 西南石油大学 High-density low-friction fracturing fluid
CN102702424A (en) * 2012-05-25 2012-10-03 西南石油大学 Zwitterionic polymer, preparation method of zwitterionic polymer and application in hydrochloric acid-base fracturing fluid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102676148A (en) * 2012-05-25 2012-09-19 西南石油大学 High-density low-friction fracturing fluid
CN102702424A (en) * 2012-05-25 2012-10-03 西南石油大学 Zwitterionic polymer, preparation method of zwitterionic polymer and application in hydrochloric acid-base fracturing fluid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
谢长宇: "耐冲刷、长效聚季铵型阳离子粘土稳定剂的研制", 《石油化工应用》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10351760B2 (en) 2014-07-15 2019-07-16 Halliburton Energy Services, Inc. Polymeric ionic liquid clay control agents
CN108329902A (en) * 2018-01-23 2018-07-27 中国石油天然气股份有限公司 A kind of salt tolerant clay stabilizer and preparation method thereof of oil field water outlet preparing fracturing fluid
CN111471440A (en) * 2020-05-28 2020-07-31 陕西科技大学 Multi-cation anti-swelling agent and preparation method and application thereof
CN111471440B (en) * 2020-05-28 2022-03-29 陕西科技大学 Multi-cation anti-swelling agent and preparation method and application thereof
CN112251213A (en) * 2020-10-15 2021-01-22 中国地质科学院水文地质环境地质研究所 Composite chemical stimulant in geothermal system
CN112251213B (en) * 2020-10-15 2022-09-23 中国地质科学院水文地质环境地质研究所 Composite chemical stimulant in geothermal system
CN114989801A (en) * 2022-06-15 2022-09-02 胜利油田华滨化工有限责任公司 Small cation clay stabilizer and preparation method thereof

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